CA2064802C - Copolymerized anthraquinone-polyester color concentrates - Google Patents

Abstract

Disclosed are color concentrate compositions which comprise a polyester having copolymerized therein at least 0.5 weight percent of an anthraquinone colorant compound having formula (I), wherein AQ is a 1,5- or 1,8-anthraquinonylene radical; R1 and R2 are the same or different and are unsubstituted or substituted alkyl, cycloalkyl or aryl; and X is a group reactive with at least one of the functional groups of the monomers from which the polyester is prepared. Amorphous polyesters and par-tially-crystalline polyesters are preferred embodiments of the color concentrates. Also disclosed are colored semicrystalline powders which may be obtained from the amorphous and partially-crystalline color concentrates by a dissolution-crystalli-zation-precipitation procedure.

Description

WO 91/03508 PCr/US90J04912 2~848~2 1 - .
CopoLyMERIzED ANTHRAQUINONE-POLYESTER COLOR CONCENTRATES
This invention pertains to polyester color concentrates comprising a polyester having copolymerized 5 therein colored residues of at least Dne polyester-reactive, t~ 1 y-stable anthraquinone compound . The color concentrates may be used to impart bluish-red shades and colors to various polymeric materials, shaped articles fabricated of and coatings formulated from such 10 polymeric materials and, especially, cosmetics ~nd home care products where non-extractability of the colorant material is an important consideration. This invention also pertains to colored semicrystalline powders derived from the color ooncentrates.
Plastics, paints, printing inks, rubber, cosmetics and simil2r materials typically are colored by organic pigments when superior brilliance and tinctorial strength are important. Toxicity considerations have been a chronic problem relative to the use of organic 20 pigments since some have been shown to be potential carcinogens and to cause contact dermatitis. Plastics usually contain various additives such as fillers, plasticizers, colorants, etc. The polymeric base of such plastics normally does not produce allergic or 25 other adverse reactions by themselves but leachable or extrActable additives are known [Fregert, Nanual of Contact Dermatitis, Munkaard Denmark (2nd Ed. 1981) ] to cause contact dermatitis.
The color concentrates provided by this invention 30 have the colorants incorporated into the polymer chain 60 that the colorant will not be leachable, sublimable or extractable and will not migrate or exude from compositions colored with the color concentrates. The colored semicrystalline powders of our invention may be 35 formulated into a wide variety of products such as*

WO 9l/03508 PCr/US90/04912 t'? ~
~,Q64~~ - 2 -cosmetics, household care products ana the liXe which do not pose any risk or hazard to humans since exposure to toxic molecules which may be abscr~ed by the body is essentially eliminated-- The amorphous and semi-5 crystalline color concentrates are preferred foI _coloring thermoplastic polymeric materials such as polyesters, polycarbonates, polyamides, cellulose esters, polyurethanes, polyolefins, eto. by conventional nelt or solution blending techniques.
It is known to color thermoplastic polymeric materials using color concentrates consisting of physical admixtures of polymers and colorants. ~owever, the use of such physical admixtures to color polymeric materials such as polyesters, e.g., poly~ethylene terephthalate) and blends thereof, presents a number of problems:
~1~ Colorant migration during arying o~ the colored polymer pellets.
~2) Colorant migration auring extrusion ana colorant accumulation on dies :which can cause film rupture and shut-downs for clean-up, etc.
Such colorant migration and accumulation result in time consuming and difficult clean-up when a polymer of another color is subseguently processed in the same equipment.
(3~ Colorants may not mix well, for example, when using two or more color concentrates to obtain a particular shaae.
( 4 ) Colorants may dif f use or exude during storzge of the colored polymeric material.
Japanese Patent 72-13,384 discloses the coloration of polyesters for use in manufacturing colorea fibers by incorporating certain anthraquinones bearing one or two reactive groups in the monomers from which the 35~, polyesters are prepared. ~he reactive groups are WO 9l/03508 PCr/US90/04912 .
2~fid~2 present on the alkyl moiety of alkylamino groups and have the formula -X-R-O-Y wherein X i5 NH or O, R is alkylene and Y is H or acetyl. These reactive anthr2quinone compounds, i . e ., those disclosed in Japanese Patent 72-13, 384, decompose and, as a result, change color when they are added early in the synthesis of polyesters , e . g ., prior to the polycondensation step .
Decomposition results in a shift in the visible absorption curve and a loss of light absorption at the desired wavelength. It also is known that low concentrations, e.g., up to 5000 parts per million, of other ~nthraquinone compounds can be reacted with or copolymerized in polyesters to produce a colored polyester material from which the anthraquinone = colorant is non-extractable. See, for example, U.S.
Patents 4,267,306, 4,359,570 and 4,403,092. Typically, an anthraquinone compound bearing one or more polyester-reactive groups , e . g ., hydroxyl , carboxy or alkoxy-carbonyl, is reacted into the polyester at some stage of the polyester's preparation. Thus, it is essential that the reactive anthraquinone compound be stable at the high temperatures, e.g., up to 300C, employed during the manufacture of high molecular weight, linear polyesters .
The color concentrates provided by this invention comprise a polyester having copolymerized therein at least 0 . 5 weight percent, based on the weight of the polyester, or more of the residue of one or more anthraquinone compounds having the formula Q (NH CH2 f-CH2-X)2 (I) wherein AQ is a 1,5- or 1,8-anthraquinonylene radical, i . e ., radicals having the structure WO 9l/03508 PCI/US90/04912 O ~ ~
5 T ~ t and - 7 ~ t 10~7~
Rl and R2 are the same or different and are unsubstituted or substituted alkyl, cycloalkyl or aryli ~nd X is a group reactive with at least one of the functional groups of the monomers from which the polyester is prepared.
The anthraquinone compounds of formula (I) and the reacted residues thereof possess the advantage of being 20 sufficiently t~ lly stable to permit their copolymerization with polyesters by adding them at the start or at an early stage of the polyester preparation.
Neither the anthraquinone compounds nor their reacted residues sublime under polymerization conditions and the 25 residues are not e~tractable from the polyesters. ~he thermal stability of the anthraquinone compounds is particularly important in the preparation of the color concentr~tes, i.e., polyesters containing from 0.5 to as high as 55 weight percent of anthraquinone colorant 3 o residue . The color concentrates are advantageous in that the colorant moiety (1) is stable to light, heat and chemicals, (2) is resistant to sublimation, heat migration, bleeding and leaching by solvents, (3) possesses high color value or chroma ana visibIe light 35 absorption characteristics which allows the color concentrates to be combined with yellow and/or blue ~ cyan ) color concentrates to provide a range of colors, (4 ) is safe to humans and the environment .
The nitrogen atom of -NE- of the reactive group ~l --NE-CH2 -f -CE2-x WO 9l/03508 PCr/US90/04912 F~ ' - - =
~ - ~06~8~
5 -- =.
i8 bonded directly to a nuclear atom, i.e., a ring carbon atom, of anthraquinone nucleus AQ The reactive anthraquinone compounds function as a copolymerizable monomer and are present within the polymer chain of the 5 polyester , e . g ., IR~
--X' -CH2-~-CH2-NH--AQ--NH-CH2-~-CH2-X' -Polyester--wherein AQ, R1 and R2 are defined above and X' is the residue of reactive substituent X, e.g., -O-, 15 -CO-, -NH-, etc.
The alkyl, cycloalkyl and aryl radicals represented by R1 and R2 may be unsubstituted or substituted and m~y 20 contain up to 10 carbon atoms. R1 and R2 preferably are e2ch lower alkyl , i . e ., alkyl of up to 4 carbon atoms , especially methyl.
Examples of the reactive groups which X may represent include hydroxy, carboxy, an ester radical, 25 amino, alkylamino, and the like. The ester r~dicals may be any radical having the formula -o-C-R3, -o-C-o-R3, -o-CNH-R3 or -~-o-R3 30 wherein R3 is an unsubstituted or substituted alkyl, cycloalkyl or~aryl radical, preferably unsubstituted alkyl, e . g ., alkyl of up to 8 carbon atoms, or phenyl, and most pref erably , lower alkyl , e . g ., methyl and ethyl. Reactive group X preferably is hydroxy or 35 alkanoyloxy of up to 4 carbon atoms, e.g., acetoxy.
Reactive radical ~1 4 0 NH CH2 ~ CH2 X
most preferably is 2,2-dimethyl-3-hydroxypropylamino.
4 5 The anthraquinone compounds described hereinabove may be prepared using known procedures ~nd anthraquinone WO 91/03508 ~ ~ PCI/US90/04912 - , ,,", reactants, or procedures and/or reactants analogous thereto, wherein an anthraquinone reactant containing amine-displaceable groups is: reacted with an amine:

AQ--(Y ) 2 + H2N-CH2-¢-CH2-X --> ( I ) ~ ~2 (II) (III) wherein Y is a displaceable substituent such as 15 halogen, nitro and sulfo :and AQ, Rl, R2 and X are defined above. Typical synthesis pro~edures are described in E. Barnett, Anthracene and Anthraquinone, Bailliere, Tindall and Cox, LgPdon, 1921; H. A. I.ubs, Editor! The Chemistry of Synthetic Dyes and Piqments, 20 Reinhold Publishing Corporation, New York, 1955; and H. E. Fierz-David and L. Blangley, Fundamental Process of Dye Chemistry, Interscience Publishers, Inc., New Ygrk, 1949. The preferred anthraquinone reaetants (II~ are 1,5- and 1,8-dichloroanthraquinone.
25 Displacement of halogen may be carried out by heating a dihaloanthraquinone with excess amine (III) at about 125 to 130C for several hours. ~ Solvents such as glycol ethers, diglycol ethers, N,N-dimethylformamide, aleohols, tetrahydrothiophene-S,S-dioxide (sulfolane) 30 :and *he like may be used advantageously. T~e use Qf zcid acceptors such as sodium carbonate, sodium bicarbonate, sodium acetate=and the like, other than excess amine (III), may be advantageous in the synthesis of some compounds. Dinitroanthraquinone reactants 35 usually are reacted as a mixture of the 1,5- and 1,8-isomers to produce isomeric mixtures of anthraquinone compounds of formula (I ) .
Anthraquinone compounds of formula (I ) wherein X is hydroxy may be converted to eompounds in which X is a 40 different reactive qroup. Thus, hydroxy group X may be converted to an ester group by the re~ction o~ the .. . . _ _ _ _ _ : . _ _ _ _ _ _ _ _ _ .. _ .. _ . ...

WO 9l/03508 PCr/US90J04912 ~ - 20648~2 :5=

former group with various acylating agents such as carboxylic acid chlorides, carboxylic acid anhydrides, chloroformate esters, isocyanates and the like. The hydroxy group may be converted to a halogen substituent 5 with a halogenAting agent such as a thionyl halide or~
phosphorus oxychloride followed by reaction with ammonia to obtain the compound wherein X is amino. The halogen-substituted compound also may be reacted with an inorganic cyanide such as an alkali cyanide to obtain an 10 intermediate nitrile which can be hydrolyzed under acidic conditions to obtain anthraquinone compounds of f ormula ( I ) wherein X is carboxy Amines of formula ~III) are known compounds and/or can be prepared by published procedures. Generally, the 15 amines may be obtained by reacting an aldehyde with ammonia at elevated pressures and temperatures in the presence of a hydrogen and a hydrogenation catalyst such as Raney nickel: -2 0 ~,~1 NH
~0 - CH2 - ~ - CE~O E~ ( I I I ) (IV) wherein R1 and R2 are~defined above [U.S. Patent 2,618,658]. Aldehydes (IV) may be synthesized by the condensation of a branched-chain aldehyde with formaldehyde in the presence of a base such as sodium or potassium carbonate according to well-known processes [E. T. Stiller et al, J. Amer. Chem. Soc., 62, 1785 35 (1940 ) ] . Another means for the preparation of amines (III) involve~ the reaction of di-substituted propiolactones with hydrazine to give the corresponding hydr~zides which are converted to amines (III) upon reduction [B.I.R. Nicolaus, J. Org. Chem., 26, 2253 (1961) ]

WO 91/03~08 PCI/US90/04912 -- ` 2 ~ 6 4 ~ O ~ ~
.

The reactive apth}aquinone compounds of formula (I) and their preparation are further; 1 lust~ated by the fo~lowing examples. :
EXAMPLE 1 ___ _ __ _ _ _ A mixture of 1,5-dichloroanthraquinone (138.0 g, 0.5 mol), 3-amino-2,2-dimethylpropanol (206.0 g, 2.0 mol) and 2-ethoxyethànol (1 L) is heated at about 130C
for 22 hours with good agitation. The dark red reaction mixture is cooled to about 40C and demineralized water 10 (3 L) ~s adde~to precipita'ce the product, 1,5-bis-[ ( 3 - hydroxy -2-, 2 - dimethylpropyl ) amino ] anthraquinone, which is collec~ed by filtration, washed with demineralized water and air dried to yield 203 . 0 g of product (99~ of theory). Highly crystalline product (168 g, 829~ of theory) is ob~ained by reslurrying the crude product in hot methanol, cooling the slurry to room temperature, collecting the solids by filtration, washing with methanol and drying in air. Further purification, if ~equired, is accomplished by heating one part of the product in ten parts N,N-dimethyl-formamide in the presence of charcoal, filtering hot, cooling, collecting by f iltration, washing with methanol and drying in air. The structure of the product iS
supported by mass spectrometry. The product exhibits a ~max at 528 nm (~ max=14,662) in methylene chloride_ A mixture of 1,8-dirhlflr~-~n~hraquinone (13.8 g, 0.05 mol), 3-amino-2,2-dimethylpropanol (20.6 g, 0.20 mol) and 2-ethoxyethanol (100 mL) is heated at about 130C for 20 hours. The reaction mixture is drowned into water ( 1 L ) and the mixture is acidif ied with concentr~ted hydrochloric acid. I'he product, 1,8-bis[(3-hydroxy-2,2-dimethylpropyl)amino]anthraquinone, is obtained in an essentially quantitative yield by 35 = filter, ng, washing with wat~r and drying in air WO 91~03508 PCr/US90/04912 ~ - 2û64802 g `; , ~, Recrystallization from toluene, followed by filtration, washing with hexane and air drying gives 16 . 0 g of purified crystalline product. The product may be purified further by recrystallizati4n from methanol.
5 Thin layer chromatography shows that the product contains only one colored component and mass spectrometry analysis is consistent with 1, 8-bis [ (3-hydroxy - 2, 2 - dimethylpropyl ) amino ] anthra quinone . The bluish-red product has an absorption maximum at 556 nm and an extinction coefficient () of 12,228 in methylene chloride .
COMPARAT IVE EXAMPLE 1 _ ~
A mixture of 1,5-dichloroanthraquinone (138.0 g, 0.50 mol), ethanolamine (200 g, 3.3 mol) and 2-ethoxy-15 ethanol (1.0 L) is heated at reflux for 20 hours withgood stirring. The dark red reaction mixture is cooled and demineralized water ( 1. 5 L ) is added to precipitate the product, 1,5-bis(2-hydroxyethylamino)anthraquinone, which is collected by filtration, washed with water (500 20 mL) and then methanol (500 mL) and dried in air. The product is purified by recrystallizing from N,N-dimethylformamide (2 L) in the presence of charcoal.
The yield is 104 g (63.8~ of theory) of pure product which has an absorption maximum at 520 nm (~=13,667) 25 in the visible absorption spectrum in N,N-dimethylf ormamide .
Additional anthraquinone compounds which may be utilized in the preparation of our novel color concentrates are set forth in Table I. These compounds 3 0 may be prepared by the procedures ref erred to herein and conform to formula (I). The heading "Positions" in Table I refers to the positions of the reactive group Q6480~ --. ~
5 -N~-CH2-~-CH2-X
the ~nth ~q in n~ nucle~.

WO 91/03508 PCI`JUS9OJ049~2 - 11 - 20~8-~2 ., 'n Lr~ m 'n n m n In n m m n n m n m r~
x ~, x 5 5 1 5 5~ 5 0 x C x ~ ~ O ~ x w O O c~ x 5 o ' ' ~, C
N
~ n 5 C~) 5 D X
N 5 x x 5' x tr~ 5~ 5~ 5, 5~ ~ x ~ 5 ' x ;I XD n XD XD
~J ' ,.
r~ n ~D 1~ o ~ ~ r) ~r m ~D 1-- ~
~1 ~ ~1 ~I r-l ~I rt r-l rt -~- 2064~0~ ~ .

5 ~ C~ ~'I L~ ~ 3 ~ ~ m ~ ~ 5 (~ 5 ~ ~ 1 5~ ` 5' 5' 5~ 5~ 5~ ~ 5~ 5~ 5' 5~ 5 u-) ~ 5 ~_) 5 ~' WO 91/0350~ PCT/US90/04912 CD ~D D ~ ~ ~ rD ~ J ~D O ~ ~D ~ ~D
5~ ~ 5' 5' ~ A 5' --~ 5`~ 5 ~
V c G o c c 5~ ~
~, 5. 5' 5. 5' C~ 5' 5' 5' 5' 5' 5' 5' 5, 5~ ~ V ' ' I -rl , ~') 5. ~_) ~1 5 D
5' r . ~D 1~ O r~ r n ~D 1-- ~D O~ O r~ ~

.

The color concentrates of the present invention comprise crystalline, semi-crystalline and amorphous polyesters having copolymerized therein at least 0 . 5 weight percent of the residues of at least one 5 ~nthraquinone compound of formula ~I ) . The concentration of thè ànthraquinone residue in the polyester is dependent on such factors as the end use for which a particular concentrate is designed, the polyester being used and the physical characteristics 10 required of the color concentrate. Normally, the color concentrates will not contain more than 55 weight peTcent of anthraquinone residues with a concentration in the range of 10 to 40 weight percent being more common. Typically, the polyester color concentrates have an inherent viscosity of at least 0 . 20 and arë- - -comprised of ~i) a diacid component consisting of the residues of one or more dicarboxylic acids, ~ ii ) a diol component consisting of ~he residues of one or- more.
diols and ~iii) a colorant component consisting of the 20 residues of one or more anthraquinone compounds of f ormula ~ I ) . The concentration of colorant component (iii) and inherent viscosity are interrelated to the extent that the degree of polymeri~ation and the inherent viscosity should be sufficiently high to ensure 25 that substantially all of the colorant compound is ~
reacted into the polymer and, preferably, into polymer chains which are not extractable. Thus, for example, when the concentration of colorant component ~ iii ) is 20 weight percent or higher j the inherent viscosity of the 30 polyester normally will be 0 . 25 or higher The diacid r~ s may be.derived from aliphatic, ~licyclic, or aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 1,4-cyclohexane-dic~rboxylic acid, 1,3-cyclohexanedicarboxyllc acid, 35 succinic acid, glutaric ~cid, adipic acid, sebacic ~cid, WO 9l/03508 PCI`/US90/04912 2~6~8~2 l,12-dodecanedioic acid, 2,6-naphthalenedicarboxylic acid and the like. In the polymer preparation, it is often preferable to derive the diacid residues from an ester-forming derivative of the dicarboxylic acid such 5 as the dimethyl, diethyl, or dipropyl esters. The anhydrides or acid halides of these acids also may be employed where practical.
The diol components of the described polyesters may be selected from ethylene glycol, I,2-propanediol, 1,3-propanediol, 1,4-~utanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-cyclohexanediol, 1,4-cyclo-hexanediol, 1, 2 - cyclohexanedimethanol, 1, 3 - cyclo -hexanedimethanol, 1,4-cyclohexanedimethanol, X, 8 - bis ( hydroxymethyl ) - tricyclo - [ 5 . 2 . 1. 0 ] - decane where in X represents 3, 4, or 5; and diols containing one or more oxygen atoms in the chain, e.g., diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 1,3- and 1,4-bis(2-hydroxyethyl)benzene and the 20 like. In general, these diols contain 2 to 18, pref erably 2 to 12 carbon atoms . Cycloaliphatic diols can be employed in their cis -or trans conf iguration or as mixtures of both forms.
The amorphous color concentrates of our invention 25 exhibit a glass transition temperature (Tg) and no, or only a trace of, crystallization or melting point by differential scanning calorimetry (DSCj. Examples of such amorphous polyesters include those obtained by the polymerization of an anthraquinone compound of formula 30 (I), terephthalic and/or~ 2,6-naphthalenedicarboxylic acid and a branched-chain diol having the formula ~1 3 5 HO - CH2 - ~ - CH 2 ~ OH

6~

wherein R1 and R2 are defined hereinabove. Preferred amorphous polyester color eoncentrates have an inherent viscosity of 0.2 to 0.8 and are comprised of:
(i)diacid residues comprised of at least 50, preferably ~t least 80, mole percent terephthalic and/or 2, 6-naphthalenedic~rboxylic acid residues;
(ii) diol residues comprised of at least 50, preferably at least 80, mole percent of residues of a diol having the f ormula . 1 ~O - C~ - - CH - O~

wherein R1 and R2 are the same or different and are lower alkyl; and (iii) residues of anthraquinone compound (I).
The particularly preferred amorphous polyester color concentrates are comprised of ~ i ) diacid residues eonsisting essentially of terephthalic and/or~ ~
2, 6 -naphthalenedlcarboxylic a~cid residues; diol ~ ~
residues consisting essentially of 2,2-dimethyl-1,3-propanediol resldues, and tiii) resldues of --anthraquinone compound ( I ), especially an anthraquinone compound having the f ormula ~ AQ--(NEI-CE2-~-C~2 ~)2 35 wherein AQ is a 1,5- or 1,8-anthraquinonylene radical.
Other amorphous polyesters, as def ined above, suitable for preparing the colored semicrystalline powders may be obtained by employing ~ i ) two dicarboxylic acids and one or more diols or ~2) two 40 diols and one or more dicarboxylic acids according to known procedures for obtaining amorphous polyesters_ The polyester comprising a diacid component eonsisting of ~5 mole pereent terephtha~ie aeid residues and WO 91/03508 PCI~/US90~04912 2~ g~2 .
25 mole percent 1,4-cyclohexanedicarboxylic acid residues, a diol component consisting of 1,4-butanediol residues and residues of anthraquinone compound (I) is an example of such a polyester.
The partially-crystalline color concentrates of this invention usually exhibit a glass transition temperature, a crystallization temperature and a melting temperature by DSC_ These partially-crystalline, poly-ester concentrates are comprised of ( i ) diacid residues consisting of at least 80 mole percent terephthalic acid residues, 2, 6-naphthalenedicarboxylic acid residues, 1, 3-cyclohexanedicarboxylic acid residues, 1, 4 -cyclo-hexanedicarboxylic acid residues or a mixture thereof, ( ii ) diol residues consisting of at least 50 mole percent of residues having the formula ~--(CH2 )m{)~
wherein m is 4 to 12 and ( iii ) residues of colorant compound (I). A preferred partially-crystalline color concentrate has a melting temperature of at least 110C
and is comprised of ( i ) diacid residues comprised of at least 80 mole :percent terephthalic acid residues, (ii) diol residues comprised of at least 80 mole percent of residues of 1,4-butanediol and (iii) residues of colorant compound (I). An especially preferred partially-crystalline color concentrate has a melting temperature of at least 110C and consists essentially of (i) terephthalic acid residues, (ii) 1,4-butanediol residues and (iii) residues of 1,5-~is[(3-hydroxy-2,2-dimethylpropyl ) amino ] anthraquinone .
The colored semicrystalline powders provided by our invention may be obtained by means of a dissolution-crystallization-precipitation procedure wherein the amorphous or partially-crystalline polyester color concentrates described above are dissolved in an organic ~
solvent from which the polymeric color concentrate is recovered in a finely diviaed form consisting of : - 13 -.
particles of relatively uniform size, e. g ., from lO to 30 microns. If desired, the particle size of the colored semicrystalline powders may be reduced further by conventional grinding processes. Examples of 5 solvents in which the amorphous and/or partially-crystalline concentrates may be dissolved include halogenated hydrocarbons such as aliphatic chlorides, e.g., methylene chloride, esters such as alkyl esters of carboxylic acids , e . g ., ethyl acetate and methyl lO benzoate, hydrocarbons such as toluene and ethers such as tetrahydrofuran. We have found methylene chloride to be a particularly effective solvent.
The particular dissolution-crystallization-precipltation procedure util~ized is not critical. The 15 amorphous or partially-crystalline concentrate may be dissolved in a suitable solvent at eLe~ated temperatures and then crystallized in a finely-divided state by cooling, with or without a reduction in the volume of solvent , i . e ., either with or without a solution 20 concentration step. Another useful technique involves dissolving the amorphous concentrate in an organic~
solvent, either at ambient or elevated temperature, ~nd then adding to the solution another miscible-solvent which causes crystallization of the colored 25 semicrystalline powder. The use of methylene chloride as the primary solvent and an alkyl acetate such as ethyl acetate as the "crystallization-inducing" solvent has been found to be particularly efficacious.
Depending on their intende~ utility, the co~ored 30 semicrystalline powders may be extracted with a suitable organic solvent to remove relatively low molecular weight polyester oligomers. Examples of oligomer-extracting solvents include ketones such as acetone, 2-pentanone, 3-methyl-2-butanone, 4-methyl-2-35 pentanone, 2-hexanone and 5-methyl-2-hexanone;

WO 91/03508 PCr/US90/04912 g~

hydrocarbons such as hexane, heptane and toluene; and ethers such as tetrahydrofuran. Another, but not preferred, dissolution-precipitation procedure involves dissolving the amorphous color concentrates in certain 5 solvents, e. g ., ethyl acetate, from which the polymeric color concentrate, after undergoing a change in morphology, precipitates.
The dissolution-crystallization-precipitation procedure alters the morphology of the amorphous and 10 partially-crystalline polyester color concentrates in a number of respects. X-Ray diffraction analysis of the colored semicrystalline powders shows a marked increase in the crystallinity of the polyester and, while the amorphous polyester concentrates do not exhibit a 15 melting temperature, the microcrystalline conce~trates usually ~almost always) exhibit a melting temperature by DSC. Although the weight average molecular weight (Mw) may increase, decrease or not be changed by the dissolution-crystallization-precipitation procedure, the 20 number average molecular weight (Mn) always increases, the magnitude of the increase depending on the degree to which oligomeric material has been removed from the colored semicrystalline polyester powder. The polydispersity ratio (Mw:Mn) of the colored semi-25 crystalline polyester is always less than that of thepolyester concentrate from which it is prepared due to the increase in Mn (even when Mw incre-ases, Mn increases more). Finally, the inherent viscosity of the colored semicrystalline powders normally is slightly higher than 3 0 that of the color concentrate .
Processes for preparing finely divided~ forms of polyesters also are disclosed in U . S . Patents 4,378,228, 4,254,207, 3,586,654, 3,931,032, 4,267,310, 4,305,864, 4,451,606, 3,674,736 ana 3,669,922. The 35 amorphous and partially-crystalline polyester color _ _ .. .. . _ _ .. . .. . .. _ _ _ , . .. .. . . .

concentrates may b~ used in coloring ~ various thermoplastic polvmeric materials when non-extractability or non-volatility of the colorant is critical because of toxicity considerations, e.g., in rigid and flexible packaging matelials for food. The concentrates and powders may be used in formulating inks, coatings, toners f or impactless printing, and similar products.
Our novel color concentrates and their preparation are further~ illustrated by the following examples. The inherent viscosities specified herein are determined at 25C using 0 . 5 ~ of polymer ~polyester color concentrate) per 100 mL of a sol~rent consisting of 60 weight percent phenol and 40 weight percent tetrachloroethane. The weight average molecular weight (Mw) and number average molecular weight values referred to herein are determined by gel permeation chromatography. The melting temperatures are determined by differential scanning calorimetry on the first and/or second heating cycle at a scanning rate of 2QC per minute and are reported as the peaks of the transitions .
EXAMPLE 53 ~ ~
The following materials are placed in a 500-mL
three-necked, roun~-bottom flask:
133.6 g (0.689 mol) dimethyl terephthalate 85.5 g (1.380 mol) ethylene glycol 0 . 0178 g Ti from a n-butanol solution of titanium tetraisopropoxide 54 . 0 g ( 0 .132 mol ) 1, 5 -bis [ ( 3 -hydroxy- 2, 2 -di-methylpropyl ) amino] anthraquinone The flask is equipped with a nitrogen inlet, stirrer, vacuum outlet, and condensing flask. The flask and contents are heated in a ~elmont metal bath with a nitrogen sweep over the reaction mixture as the .. . . .

~ 2064802 temperature is increased to 200C and then to 220OC over 75 minutes. Over the next 30 minutes the temperature is increased to about 240C and then to about 260C over the next 30 minutes. The temperature is quickly raised (over about 10 minutes) to 275C and a vacuum is applied until the pressure is reduced to 0. 067 kPa. The poly--~!r n~n~ation iS completed by heating the flask and contents at about 275C for about 45 to 60 minutes under a pressure of 0 .1 to o . 5 mm Hg . The f lask is removed from the metal bath and is allowed to cool while the polymer solidifies. The resulting dark red polyester, containing 3 0 . 3 weight percent of the anthraquinone colorant residue, has an inherent viscosity of o . 49 .
F~AMPI~ 54 The following materials are placed in a 500--mL
three--necked, round--bottom f lask:
135.8 g (0.70 mol) dimethyl terephthalate 94.6 g (0.91 mol) 2,2--dimethyl--1,3--propanediol 0 . 0177 g Ti from a n--butanol solution of titanium tetraisopropoxide 18.0 g (0.044 mol) 1,5--bis[ (3--hydroxy--2,2--di--methy lpropy 1 ) amino ] anthraquinone The flask is equipped with a nitrogen inlet, stirrer, vacuum outlet, and condensing flask. The flask and contents are heated in a Belmont metal bath with a nitrogen sweep over the reaction mixture as the temperature is increased to 200C and then to 220C over 9 0 minutes . Over the next 3 0 minutes the temperature is increased to about 240C and then to about 260C over the next 30 minutes. The temperature is quickly raised (over about 10 minutes) to 275C and a vacuum is applied until the pressure is reduced to 0. 067 kPa. The pc~ly~-on~ n~ation is ~:ompleted by heating the flask and contents at about 275C for 75 minutes under ~ pressure 35 of 0. 013 to 0. 067 kPa. ~h~ flask is removed ~rom the WO 91/03508 PCr~US90~04912 ~ - 2a64802 metal bath and is allowed to cool while the polymer solidifies. The resulting dark red polyester, con~aining 30 . 3 weight percent of the anthraquinone colorant residue, has an inherent viscosity of 0.56, no 5 melting temperaturç,- a weight average molecular weight of 39,000, a number averagç molecular weight of 20,000 and a polydispersity value of 1. 94 .
EXANPLE 5 5 ~ ~
A portion (a5.0 g) of the amorphous polyester color 10 concentrate prepared in Example 54 is granulated using a Wiley mill and dissolved in methylene chloride (200 mL) at about 25C with stirring. Ethyl acetate (200 mL) is added and the methylene chloride is removed by distillation. The mixture is stirred for about 12 to 15 15 hours (usually overnight) at about 25C during which time the colored semicrystalline powae~r separates.
Acetone (200 mL) is added with stirring and the solid is collected by filtr~tion and slurried in acetone (200 mL
and filtered four times to remove oligomers from the 20 product wXich after drying weighs 23 . 6 g. The colored semicrystalline powder thus prepared has an inherent viscosity of 0.5B, a melting temperature of 144C, a weight average molecular weight of 38,000, a number average molecuIar weight of 25, 000 and a polyaispersity 25 value of l . 52 . The accountability of the anthraquinone colorant compound is 93~ as detf~rmi nf--l by visual spectroscopy and a comparison of the absorbance of a methylene chloride solution of 1,5-bis[(3-hydroxy-2,2-dimethylpropyl)-amino]anthraquinone with the absorbance 30 of a methy~ene chloride solution of the microcrystalline color concentrate. The comparison shows no shift in absorbance indicating that the colorant is not decomposed during the synthesis of the polyester.
,, `: .

WO 9l/03S08 PCl`/US9OJ04912 The procedure of Example 54 is repeated using:
108.6 g (0.560 mol) dimethyl terephthalate 75.7 g (0.728 mol) 2,2-dimethyl-1,3-propaDediol 0 . 0170 g Ti from a n-butanol solution of titanium tetraisopropoxide 52.D g (0.44 mol) 1,5-bis[(3-hydroxy-2,2-di-methylpropyl)amino] anthr~quinone ~he dark red polyester color concentrate contains 30 . 6 weight percent oi the residue of 1,5-bis[(3-hydroxy-2,2-dimethylpropyl)amino]anthraquinone and has an inherent viscosity of D.47, a weight average molecular weight of 31,000, a number average molecular weight of 17,000 and a polydisperslty value of l . ~34 .

The procedure described in Example 55 is repeated precisely using 25 . 0 g of the color concentrate prep~red in Example 56 to give 22 . 4 g of dark red, semi-crystalline powder having an inherent viscosity of 0.49, a weight average molecular weight of 35, 000, a number average molecular weight of 25, 000 and a polydispersity value of 1. 42 . The accountability of the anthraquinone colorant by visual spectroscopy is 91.196.

A portion (57.2 g) of the color concentrate prepared in Example 56 is granulated and partially dissolved in boiling ethyl acetate (480 mL) by stirring.
The mixture is cooled with stirling to 25C at a rate of less than 1C per minute. Stirring is stopped and the 3 0 color concentrate is allowed to precipitate and undergo solvent-induced crystalli~;ation for about 15 hours. The darX red crystalline solid is separated by filtration and slurried in acetone ( 300 mL ) three or four times to remove any low molecular weight oligomers f rom the 35 product. After the last ~iltration, the solid is dried WO 91/03~08 PCI/US90/04912 ~9~ --- a4 -to give 45.1 g of colorea semicrystalline powder having ~ melting temperature of 122C, a weight average molecular weight of 36,12a, ~a number average molecular weight of a6, aa4 and a polydispersity vaIue of l . 38 .
5 Color accountability, determined as aescribed in Example 55, is 93%.

The procedure of Example 54 is repeated using:
84.1 g (0.43 mol~ aimethyl terephthalate 58.6 g (0.56 mol) a,a-dimethyl-1,3-propanediol 0 . 0165 g Ti from a n-butanol solution of tit nium tetraisopropoxide 85.1 g (O,al mol) 1,5-bis[(3-hyaroxy-2,2-ai-methylpropyl ) amino] anthraquinone The extremely dark red polyester color concentrate contains 51. 6 weight percent of the residue Qf l, 5-bis-[ ( 3 - hydroxy - 2, 2 - dimethylpropyl ) amino ] anthraquinone and has an inherent viscosity of 0 . 36 .

The procedure aescribed in Example 55 is repeated precisely using 25 . 0 g of the color concentlate prepared in ExampIe 58 to give a2.9 g of very dark red, semi-crystalline po~der. - - -. . =
A portion (75.0 g) of the color concentrate prepared in Example 58 is ground and crystallized from ethyl acetate (500 mL) as describea in Example 57 to obtain 58 . 8 g of very dark rea crystalline color concentrate with an anthraquinone coIorant account-ability of 93%.

WO 9l/03508 PCl/US9OJW912 . i~o64so2 ~
_ The procedure of Example 54 is repeated using:
135.8 g (0.70 mol) dimethyl terephthalate 9 4 . 6 g ( 0 . 91 mol ) 2, 2 -dimethyl-1, 3 -propanediol 0 . 0164 g Ti from a n-butanol solution of titanium tetraisopropoxide 0 . 82 g ( 0 . 21 mol ) 1, 5 -bis [ ( 3 -hydroxy- 2, 2-di-methylpropyl ) amino ] anthraquinone The bright red polyester color concentrate contains 0 . 50 weight percent of the residue of 1,5-bis[(3-hydroxy-2,2-dimethylpropyl)amino]anthraquinone and has an inherent viscosity of 0 . 65 .

The procedure~ of Example 54 is repeated using:
113.0 g ~(0.70 mol) dimethyl 2,6-naphthalenedi-carboxylate ~ =
62.5 g (0.91 mol) 2,2-dimethyl-1,3-propanediol O . 0170 g Ti from a n-butanol solution of titanium tetraisopropoxide 51.7 g (0.127 mol) 1,5-bis[(3-hydroxy-2,2-di-methylpropyl ) amino] anthraguinone The dark red polyester color concentrate contains 30.4 weight percent of the residue of 1,5-bis[(3-hydroxy-2,2-dimethylpropyl)amino]anthraquinone and has an inherent viscosity of 0 . 37 . ~
EXAMPLE 64 _ _ The procedure of Example 54 is repeated using:
135.8 g (0.70 mol) dimethyl terephthalate 9 4 . 6 g ( 0 . 91 mol ) 2, 2 - dimethyl -1, 3 - propanediol 0 . 0164 g Ti from a n-butanol solution of ~itanium tetraisopropoxide 0 .82 g (0.21 mol) 1,8-bis[ (3-hydroxy-2,2-di-methylpropyl ) amino ] anthraquinone The dark red polyester color concentrate contains 0 . 50 weight percent of the residue of 1, 8-bis [ ( 3 -hydroxy-_ . _ _ _ _ _ _ . . . . _ _ . _ , , , _ , . .. ..

WO 9l/03508 PCI/US90/04912 - ~6480~ ~
., 2, 2 -dimethylpropyl ) amino] anthraquinone and hns an inherent viscosity of 0 . 67 .

The procedure of Example 54 is repeated using:
108.6 g (0.70 mol) dimethyl terephthalate 75.7 g (0.91 mol) 2,2-dimethyl-1,3-propanediol 0 . 0166 g Ti from a n-butanol solution of titanium tetraisopropoxide 52.0 g (0.21 mol) 1,5-bis[(2-hydroxyethyl)amino]-anthraquinone During the polycondensa~lon, a color~ change from red to orange was observed, indicating decomposition of the anthraquinone compound. The polymer produced is extremely brittle and has a 1QW inherent viscosity (0.21), further indicating decomposition of the anthraquinone colorant. Vislble spectroscopy shows the polymer to ~ontain a considerable amount of yello~-orange decomposition product in addition to the red residue of .~1,5-bis[(2-hydroxyethyl)amino]anthraquinone as the absorption curve is shifted considerably from absorption maximum (~max) at 521 nm for 1, 5-bis [ ~2-hydroxyethyl)amino]anthraquinone (in methylene chloride) to ~max 5D9 for the copolymerized colDr-concentrate.
EXAMPLE 6 5 _ _ The following materials are placed in a 500-mL
three-necked, round-bDttom flask:
145 50 g (D.750 mol) dimethyl terephthalate 101.25 g (1.125 mol) 1,4-butanediol 0~0214 g Ti from a n-butanol solution of ~ == titanium tetraisopropoxide 63.0D g (0.044 mol) 1,5-bis[(3-hydroxy-2,2-di-methylpropyl ) amino] anthraquinone The flask is equipped with a nitrogen inlet, stirrer, vacuum outlet, and condensing flask. The flask and contents are heated in a Belmont metal bath with a 2~64802 nitrogen sweep over the reaction mixture as the tempera--ture is increased to 200C. The mixture is heated at 200C for 1.75 hours and then the temperature is raised to and maintained at 225C over a period of 2.25 hours.
The nitrogen sweep is then stopped and vacuum is applied to lower the pressure to about o. 067 to 0.13 kPa. The polycondensation is completed by heating the flask and contents at about 225C for 1 hour under a pressure of o. 067 to 0.13 kPa. The vacuum is then relieved with nitrogen and methyl benzoate ( 125 mL) is added slowly and stirred to solution over about 10 minutes with the flask still in the metal bath. The resulting solution is transferred to a 2 L beaker and stirred until crystallization occurs. Hexane (700 mL) is added slowly with stirring to dilute the slurry and keep it stirable.
(Acetone, which removes more oligomeric material, also may be used. ) The diluted slurry is stirred for 30 minutes, filtered and the cake is washed with hexane.
The cake is twice reslurried in hexane and then dried in a vacuum oven. The resulting dark red semicrystalline polyester powder, containing 29 . 42 weight percent of the anthra~uinone colorant residue, has an inherent viscosity of 0.202, a melting t~ ~Lu. e of 175C, a glass transition temperature of 66C, a weight average molecular weight of 12,646, a number average molecular weight of 8359 and a polydispersity value of 1. 51.
Reslurrying the powder twice in acetone increases the non--extractability o~ color and r~ises the inherent viscosity to 0 . 26 .
3 o F:XAMPT.~ 66 The pL~,ce.luLe described in Example 65 is repeated except that the reaction mixture is heated at 200C for 1.75 hours and then the temperature is raised to 220OC
over 1.25 hours, then to 240C over 1.25 hours and finally to 270C over 1.25 hours. Vacuum is applied to _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ~

1~ ` 20648~2 lower the pressure to about 0 . 067 to 0 .13 kPa and polycr~n~l~ncation is completed by heating the flask and contents at about 270C for 22 minutes under a pressure of o. 067 to 0.13 kPa. The vacuum is then relieved with nitrogen and methyl benzoate (125 mL) is added slowly and stirred to solution over about 50 minutes with the f lask still in the metal bath. The resulting solution is transferred to a 2 L beaker and stirred until crystallization occurs . Acetone ( 1 L) is added slowly with stirring to dilute the slurry and keep it stirable.
The diluted slurry is stirred for 30 minutes, filtered and the cake is slurried in hexane (1 L). The cake is again slurried in acetone and hexane and then dried in air to yield 212.89 g (99.40% of theory) colored powder.
The dark red polyester powder, containing 29 . 42 weight percent of the anthra~uinone colorant residue, has an inherent viscosity of 0.190, a melting temperature of 172C, a glass transition temperature of 54C, a weight average molecular weight of 12, 806, a number average molecular weight of 8903 and a polydispersity value of 1.44.
EXA~qPT ~ 67 The following materials are placed in a 500--mL
thrcc ne ked, round--bottom f lask:
91. 0 g (0 . 469 mol) dimethyl terephthalate 63.3 g (0.704 mol) 1,4--butanediol 0. 01343 g Ti from a n--butanol solution of titanium tetraisopropoxide 40.0 g (0.0976 mol) 1,5--bis[(3--hydroxy--2,2~i--3 0 methylpropy l ) ami no ] anthraqui none The flask is equipped with a nitrogen inlet, stirrer, v~cuum outlet, and condensing flask. The flask and contents are heated in a Belmont metal bath with a nitrogen sweep over the reaction mixture as the 35 temperature is incre-~ed t~ ~Oo ~ and th to 20C over 2 hours . Over the next 3 0 minutes the temperature is increased to about 240C and then to about 260C over the next 30 minutes. The temperature is quickly raised (over about 10 minutes) to 275C and a vacuum is applied until the ~L~SauL~ is reduced to 0.067 kPa. The poly~n~l~n-ation is completed by heating the flask and contents at about 275C for 45 minutes under a ~es~ule of o. 013 to 0 . 067 kPa. The vacuum is then relieved with nitrogen and methyl benzoate (125 mL) is added slowly 10 and stirred to solution over about 10 minutes with the flask still in the metal bath. The resulting solution is transferred to a 2 L beaker and stirred until crystallization occurs. Acetone (500 mL) is added slowly with stirring to dilute the slurry and keep it 15 stir2ble. The diluted slurry is stirred for 30 minutes, f iltered and the cake is washed with acetone . The cake is twice reslurried in acetone and then dried in air.
The resulting dark red semicrystalline polyester powder, containing 29 . 77 weight percent of the anthraquinone 20 colorant residue, has an inherent viscosity of 0.485, a melting temper~ture of 182C, a weight average molecular weight of 36,927, a number average molecular weight of 23, 685 and a polydispersity value of 1. 59 .
The invention has been described in detail with 25 particular reference to preferred ~ho~ ts thereof, but it will be understood that variations and modi~ica--tions can be effected within the spirit and scope of the invention .
.

Claims (28)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A color concentrate comprising a polyester having copolymerized therein at least 0.5 weight percent, based on the weight of the concentrate, of the residue of one or more anthraquinone compounds having the formula wherein AQ is a 1, 5-- or 1, 8--anthraquinonylene radical;
R1 and R2 are the same or different and are C1--C10--alkyl, C3--C10 cycloalkyl or phenyl; and X is a group reactive with at least one of the functional groups of the monomers from which the poly--ester is prepared.

2. A color concentrate according to Claim 1 comprising a polyester having an inherent viscosity of at least 0.20 having copolymerized therein at least 0.5 weight percent, based on the weight of the concentrate, of the residue of one or more anthraquinone compounds having the formula wherein AQ is a 1,5-- or 1, 8--anthraquinonylene radical;
R1 and R2 are the same or different and are C1--C4 alkyl; and X is hydroxy, carboxy, amino, alkyl amino or an ester group having the formula , , or wherein R3 is C1--C8 alkyl, C3--c8 cycloalkyl or phenyl radical.

3. A color concentrate according to Claim 1 comprising a polyester having an inherent viscosity of at least 0.20 having copolymerized therein 10 to 40 weight percent, based on the weight of the polyester, of the residue of one or more anthraquinone compounds having the formula wherein AQ is a 1, 5-- or 1, 8--anthraquinonylene radical;
R1 and R2 are the same or different and are C1--C4 alkyl; and X is hydroxy, carboxy, amino, alkyl amino or an e6ter group having the formula , , or wherein R3 is C1--C8 alkyl or phenyl.

4. A color concentrate according to Claim 1 comprising a polyester having an inherent viscosity of at least 0.20 having copolymerized therein 10 to 40 weight percent, based on the weight of the polyester, of the residue of an anthraquinone compound having the formula wherein AQ is a 1, 5-- or 1, 8--anthraquinonylene radical.

5. An amorphous color concentrate comprising an amorphous polyester having copolymerized therein at least 0.5 weight percent, based on the weight of the concentrate, of the residue of one or more anthraquinone compounds having the formula wherein AQ is a 1, 5-- or 1, 8--anthraquinonylene radical;
R1 and R2 are the same or different and are C1--C10 alkyl; C3--C8 cycloalkyl or phenyl; and X is a group reactive with at least one of the functional groups of the monomers from which the poly--ester is prepared.

6. An amorphous color concentrate according to Claim 5 comprising a polyester having an inherent viscosity of at least 0.20 comprised of:

(i) diacid residues comprised of at least 50 mole percent terephthalic and/or 2,6--naphthalenedicarboxylic acid residues;
(ii) diol residues comprised of at least 50 mole percent of the residue of a diol having the formula and (iii) residues of one or more anthraquinone compounds having the formula wherein AQ is a 1,5-- or 1, 8--anthraquinonylene radical;
R1 and R2 are the same or different and are C1--C4 alkyl; and X is hydroxy, carboxy, amino, alkyl amino or an ester group having the formula , , or wherein R3 is C1--C8 alkyl, C3--C8 cycloalkyl or phenyl radical, provided that component (iii) constitutes at least 0.5 weight percent of concentrate.

7. An amorphous color concentrate according to Claim 5 comprising a polyester having an inherent viscosity of 0.20 to 0.80 and a melting temperature of at least 110°C comprised of:
(i) diacid residues comprised of at least 80 mole percent terephthalic and/or 2,6-naphthalenedicarboxylic acid residues;
(ii) diol residues comprised of at least 80 mole percent of the residue of a diol having the formula and (iii) residues of one or more anthraquinone compounds having the formula wherein AQ is a 1,5- or 1,8-anthraquinonylene radical;
R1 and R2 each is methyl;
X is hydroxy, carboxy, or an ester group having the formula , , or wherein R3 is alkyl or phenyl, provided that component (iii) constitutes at least 0.5 weight percent of concentrate.

8. An amorphous color concentrate according to Claim 7 wherein component (iii) constitutes 10 to 40 weight percent of the concentrate.

9. An amorphous color concentrate according to Claim 5 comprising a polyester having an inherent viscosity of 0.20 to 0.80 and a melting temperature of at least 110°C comprised of:
(i) diacid residues consisting essentially of terephthalic and/or 2,6-naphthalene-dicarboxylic acid residues;
(ii) diol residues consisting essentially of 2,2-dimethyl-1, 3-propanediol residues; and (iii) residues of an anthraquinone compound having the formula wherein AQ is a 1, 5- or 1, 8-anthraquinonylene radical;
provided that component (iii) constitutes at least 0.5 weight percent of concentrate.

10. An amorphous color concentrate according to Claim 7 wherein component (iii) constitutes 10 to 40 weight percent of the concentrate.

11. A partially-crystalline polyester color concentrate comprised of:

(i) diacid residues consisting of at least 80 mole percent terephthalic acid residues, 2,6-naphthalenedicarboxylic acid residues, 1,3-cyclohexanedicarboxylic acid residues, 1,4-cyclohexanedicarboxylic acid residues or a mixture thereof;
(ii) diol residues consisting of at least 50 mole percent of residues having the formula -O-(CH2)m-O- wherein m is 4 to 12; and (iii) residues of one or more anthraquinone compounds having the formula wherein AQ is a 1,5- or 1,8-anthraquinonylene radical;
R1 and R2 are the same or different and are C1-C10 alkyl, C3-C10 cycloalkyl or phenyl; and X is a group reactive with at least one of the functional groups of the monomers from which the poly-ester is prepared, provided that component (iii) constitutes at least 0.5 weight percent of the concentrate.

12. A partially-crystalline polyester color concentrate according to Claim 11 wherein m is 4;
AQ is a 1,5- or 1,8-anthraquinonylene radical;
R1 and R2 are the same or different and are C1-C4 alkyl; and X is hydroxy, carboxy, amino, alkyl amino or an ester group having the formula , , or wherein R3 is C1--C8 alkyl, C3--C8 cycloalkyl or phenyl radical, provided that component (iii) constitutes at least 0.5 weight percent of concentrate.

13. A partially--crystalline polyester color concentrate according to Claim 11 comprised of:
(i) diacid residues consisting of at least 80 mole percent terephthalic acid residues, (ii) diol residues consisting of at least 80 mole percent of residues of 1,4--butanediol; and (iii) residues of one or more anthraquinone compounds having the formula wherein AQ is a 1,5-- or 1, 8--anthraquinonylene radical;
R1 and R2 each is methyl;
X is hydroxy, carboxy, or an ester group having the formula , , or wherein R3 is C1--C8 alkyl or phenyl, provided that component (iii) constitutes at least 0.5 weight percent of concentrate.

14. A partially--crystalline polyester color concentrate according to Claim 13 wherein component.
(iii) constitutes 10 to 40 weight percent of the concentrate.

15. A partially--crystalline polyester color concentrate according to Claim 11 having a melting temperature of at least 110°C comprised of:
(i) diacid residues consisting essentially of terephthalic acid residues;
(ii) diol residues consisting essentially of 1,4--butanediol residues; and (iii) residues of an anthraquinone compound having the formula wherein AQ is a 1,5-- or 1,8--anthraquinonylene radical;
provided that component (iii) constitutes at least 0.5 weight percent of the concentrate.

16. A partially--crystalline polyester color concentrate according to Claim 15 wherein component (iii) constitutes 10 to 40 weight percent of the concentrate.

17. A colored semicrystalline powder having an average particle size of less than 30 microns comprising a normally-amorphous polyester which has been modified by dissolution-crystallization-precipitation to impart crystallinity thereto having copolymerized therein at least 0.5 weight percent, based on the weight of the concentrate, of the residue of one or more anthraquinone compounds having the formula wherein AQ is a 1,5- or 1,8-anthraquinonylene radical;
R1 and R2 are the same or different and are C1-C10 alkyl, C3-C8 cycloalkyl or phenyl; and;
X is a group reactive with at least one of the functional groups of the monomers from which the polyester is prepared.

18. A colored semicrystalline powder according to Claim 17 comprising a polyester having an inherent viscosity of at least 0.20 comprised of:
(i) diacid residues comprised of at least 50 mole percent terephthalic and/or 2,6-naphthalenedicarboxylic acid residues;
(ii) diol residues comprised of at least 50 mole percent of the residue of a diol having the formula and (iii) residues of one or more anthraquinone compounds having the formula wherein AQ is a 1,5-- or 1,8--anthraquinonylene radical;
R1 and R2 are the same or different and are C1--C4 alkyl; and X is hydroxy, carboxy, amino or an ester group having the formula , , or wherein R3 is C1--C8 alkyl, C3--C8 cycloalkyl or phenyl radical, provided that component (iii) constitutes at least 0.5 weight percent of concentrate.

19. A colored semicrystalline powder according to Claim 17 having an average particle size of less than 30 microns comprising a normally--amorphous polyester which has been modified by dissolution--crystallization--precipitation to impart crystallinity thereto comprised of:
(i) diacid residues comprised of at least 80 mole percent terephthalic and/or 2,6--naphthalenedicarboxylic acid residues;

(ii) diol residues comprised of at least 80 mole percent of the residue of a diol having the formula and (iii) residues of one or more anthraquinone compounds having the formula wherein AQ is a 1,5-- or 1, 8--anthraquinonylene radical;
R1 and R2 each is methyl X is hydroxy, carboxy, amino or an ester group having the formula , , or wherein R3 is C1--C8 alkyl or phenyl, provided that component (iii) constitutes at least 0.5 weight percent of concentrate.

20. A colored semicrystalline powder according to Claim 17 wherein component (iii) constitutes 10 to 40 weight percent of the concentrate.

21. A colored semicrystalline powder according to Claim 17 having an average particle size of less than 30 microns comprising a normally--amorphous polyester which has been modified by dissolution--crystallization--precipitation to impart crystallinity thereto comprised of:
(i) diacid residues consisting essentially of terephthalic and/or 2, 6--naphthalene--dicarboxylic acid residues;
(ii) diol residues consisting essentially of 2,2--dimethyl--1,3--propanediol residues; and (iii) residues of an anthraqiuinone compound having the formula wherein AQ is a 1,5-- or 1, 8--anthraquinonylene radical;
provided that component (iii) constitutes at least 0.5 weight percent of the concentrate.

22. A colored semicrystalline powder according to Claim 21 wherein component (iii) constitutes 10 to 40 weight percent of the concentrate.

23. A colored semicrystalline powder having an average particle size of less than 30 microns comprising a partially--crystalline polyester which had been modified by dissolution--crystallization--precipitation to mpart increased crystallinity thereto comprised of:
(i) diacid residues consisting of at least 80 mole percent terephthalic acid residues, 2,6-naphthalenedicarboxylic acid residues, 1,3-cyclohexanedicarboxylic acid residues, 1,4-cyclohexanedicarboxylic acid residues or a mixture thereof;
(ii) diol residues consisting of at least 50 mole percent of residues having the formula -O-(CH2)m-O- wherein m is 4 to 12; and (iii) residues of one or more anthraquinone compounds having the formula wherein AQ is a 1,5- or 1,8-anthraquinonylene radical;
R1 and R2 are the same or different and are C1-C10 alkyl, C3-C10 cycloalkyl or phenyl; and X is a group reactive with at least one of the functional groups of the monomers from which the polyester is prepared, provided that component (iii) constitutes at least 0.5 weight percent of the concentrate.

24. A colored semicrystalline powder according to Claim 23 wherein m is 4;
AQ is a 1, 5- or 1,8-anthraquinonylene radical;
R1 and R2 are the same or different and are C1-C4 alkyl; and X is hydroxy, carboxy, amino, or an ester group having the formula , , or wherein R3 is C1-C8 alkyl, C3-C8 cycloalkyl or phenyl radical, provided that component (iii) constitutes at least 0.5 weight percent of concentrate.

25. A colored semicrystalline powder according to Claim 23 comprising a polyester having an inherent viscosity of at least 0.20 and a melting temperature of at least 110°C comprised of:
(i) diacid residues consisting of at least 80 mole percent terephthalic acid residues, (ii) diol residues consisting of at least 80 mole percent of residues of 1,4-butanediol; and (iii) residues of one or more anthraquinone compound having the formula wherein AQ is a 1,5- or 1,8-anthraquinonylene radical;
R1 and R each is methyl;
X is hydroxy, carboxy, or an ester group having the formula , , or wherein R3 is C1-C8 alkyl or phenyl, provided that component (iii) constitutes at least 0.5 weight percent of concentrate.

26. A colored semicrystalline powder according to Claim 25 wherein component (iii) constitutes 10 to 40 weight percent of the concentrate.

27. A colored semicrystalline powder according to Claim 25 comprised of:
(i) diacid residues consisting essentially of terephthalic acid residues;
(ii) diol residues consisting essentially of 1,4-butanediol residues; and (iii) residues of an anthraquinone compound having the formula wherein AQ is a 1,5- or 1,8-anthraquinonylene radical;
provided that component (iii) constitutes at least 0.5 weight percent of the concentrate.

28. A colored semicrystalline powder according to Claim 27 wherein component (iii) constitutes 10 to 40 weight percent of the concentrate.